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101.
Solvent effects on the electrochemistry and spectroscopic properties of alkyl- and aryl-substituted corroles in nonaqueous media are reported. The oxidation and reduction of six compounds containing zero to seven phenyl or substituted phenyl groups on the macrocycle were studied in four different nonaqueous solvents (CH(2)Cl(2), PhCN, THF, and pyridine) containing 0.1 M tetra-n-butylammonium perchlorate. Dimers were formed upon oxidation of all corroles in CH(2)Cl(2), but this was not the case in the other three solvents, where either monomers or dimers were formed upon oxidation depending upon the solvent Gutmann donor number and the number or location of aryl substituents on the macrocycle. The half-wave potentials were analyzed as a function of the number of aryl substituents on the macrocycle as well as the concentration of added pyridine to PhCN solutions of the compound, and these data were combined with data from the spectroelectrochemistry experiments to determine the stoichiometry of the species actually in solution after the first oxidation or first reduction of each compound. The results of these experiments indicate that reduction of the bispyridine adduct (Cor)Co(III)(py)(2) proceeds via the monopyridine complex (Cor)Co(III)(py) to give in each case the unligated cobalt(II) corrole [(Cor)Co(II)](-). In contrast, pyridine remains coordinated after electrooxidation, and the final product was characterized as [(Cor)Co(III)(py)(2)](+). 相似文献
102.
Smaali M. Issam Gargouri Mohamed Legoy Marie Dominique Maugard Thierry Limam Farid Marzouki Nejib 《Applied biochemistry and biotechnology》2004,112(2):63-77
The filamentous fungus Sclerotinia sclerotiorum, grown on a xylose medium, was found to excrete one β-glucosidase (β-glu x). The enzyme was purified to apparent homogeneity
by ammonium sulfate precipitation, gel filtration, anion-exchange chromatography, and high-performance liquid chromatography
(HPLC) gel filtration chromatography. Its molecular mass was estimated to be 130 kDa by HPLC gel filtration and 60 kDa by
sodium dodecyl sulfate polyacrylamide gel electrophoresis, suggesting that β-glu x may be a homodimer. For p-nitrophenyl β-d-glucopyranoside hydrolysis, apparent K
m and V
max values were found to be 0.09 mM and 193 U/mg, respectively, while optimum temperature and pH were 55–60°C and pH 5.0, respectively. β-Glu x was strongly
inhibited by Fe2+ and activated about 35% by Ca2+. β-Glu x possesses strong transglucosylation activity in comparison with commercially available β-glucosidases. The production
rate of total glucooligosaccharides (GOSs) from 30% cellobiose at 50°C and pH 5.0 for 6 h with 0.6 U/mL of enzyme preparation
was 80 g/L. It reached 105 g/L under the same conditions when using cellobiose at 350 g/L (1.023 M). Finally, GOS structure was determined by mass spectrometry and 13C nuclear magnetic resonance spectroscopy. 相似文献
103.
The formation region of the various types of layered titanium hydrogen phosphate hydrates was investigated. The materials were prepared by hydrothermal methods, treating amorphous titanium phosphate with phosphoric acid (8 to 16M) in the temperature range 175 to 250°C. The materials obtained were:α-Ti(HPO4)2·H2O,γ-Ti(PO4)(H2PO4)·2H2O, and its anhydrous formβ-Ti(PO4)(H2PO4). The structure ofβ-Ti(PO4)(H2PO4) has been determined by Rietveld powder refinement of high resolution neutron diffraction data. The structure is refined in the monoclinic space groupP21/n(No. 14). The unit cell parameters are:a=18.9503(4) Å,b=6.3127(1) Å,c=5.1391(1) Å,β=105.366(2)°;Z=4. The final agreement factors were:Rp=2.9% andRwp=3.8%. The structure ofβ-Ti(PO4)(H2PO4) is built from TiO6octahedra linked together by tertiary phosphate (PO4) and dihydrogen phosphate ((OH)2PO2) tetrahedra. The layers are held together by hydrogen bonds. 相似文献
104.
PHOTOSENSITIZATION OF MELANINS: A COMPARATIVE STUDY 总被引:3,自引:0,他引:3
Abstract— Measurements of photosensitized free-radical production and oxygen consumption have been made in several melanin systems. The melanins studied were cysteinyldopa melanin (a model for pheomelanin), natural pheomelanins extracted from red hair and from red chicken feathers, and eumelanin extracted from bovine eyes. Rose Bengal was used as photosensitizer. A significant enhancement in the rates of free radical production and oxygen consumption was found in all systems when sensitizer was present. The largest effects were found with cysteinyldopa melanin and effects on pheomelanins were shown to be greater (by factors of4–6) than on eumelanins. 相似文献
105.
John A. Powell Jong J. Whang Frederick H. Owens Roger K. Graham 《Journal of polymer science. Part A, Polymer chemistry》1967,5(10):2655-2664
Copolymers of methyl methacrylate with methyl and ethyl α-hydroxymethylacrylate and with α-hydroxymethylstyrene have been prepared with free-radical initiators at temperatures below 80°C. At higher reaction temperatures or under extrusion conditions, alcohol was eliminated and the free hydroxyl content was greatly decreased. All evidence indicates the formation of six-membered lactone groups in this post-polymerization reaction: direct evidence for their formation is lacking, however, since neither infrared nor nuclear magnetic resonance spectra could be used to detect lactonization in this system. The loss of activity from 14C ester-labeled methyl methacrylate copolymer on heating could be correlated with the extent of lactonization. The degree of lactonization is relatively less with copolymers containing higher amounts of hydroxymethyl groups. The resulting polymers exhibit higher heat distortion temperatures and decreased impact resistance when compared to poly(methyl methacrylate). Attempts were made to incorporate similar lactone structures by cyclocopolymerization with methyl methacrylate of α-methacryloxymethylstyrene or ethyl α-methacryloxymethylacrylate, but only crosslinked polymers or polymers with pendent unsaturation were found. 相似文献
106.
Roger C. Alperin 《Proceedings of the American Mathematical Society》1996,124(10):2935-2941
We classify the normal subgroups of of index less than 960; they are all congruence subgroups.
107.
We prove that the-optimal solutions of convex optimization problems are Lipschitz continuous with respect to data perturbations when these are measured in terms of the epi-distance. A similar property is obtained for the distance between the level sets of extended real valued functions. We also show that these properties imply that the-subgradient mapping is Lipschitz continuous.Research supported in part by the National Science Foundation and the Air Force Office of Scientific Research. 相似文献
108.
109.
The synthesis and the crystal properties of new selenides of formula MxMo3Se4 are described. If M = Zn, Ag, Cd, Sn and Pb, they are stoichiometric with x = 0.6; if M = Fe, Mn, Cr, V, Ti, triclinic solid solutions are observed with 0.5 < x < 0.7; if M = Cu, Co, Ni, rhombohedral solid solutions are obtained with 0 < x < 1.4 for M = Cu, 0 < x < 0.7 for M = Co and 0 < x < 0.8 for M = Ni All these phases can be deduced from the Mo3Se4 structure by introducing metal atoms into the tunnels between the “Mo6Se8” metal atom cluster configuration. 相似文献
110.
The 4,6-bis(10-mesityl-5,15-di-p-tolylporpyrinyl)dibenzothiophene (H4DPSN) free base was obtained in five steps from commercially available materials. The metalation of DPSN2- with zinc(II), copper(II), and palladium(II) led to three new homobimetallic systems, (Zn)2DPSN, (Cu)2DPSN, and (Pd)2DPSN, respectively. The cofacial structures of these molecules offer the possibility of having dioxygen molecules inside the cavity for a period of time, allowing dynamic (collisional) phosphorescence quenching to be more efficient. The bimolecular excited-state deactivation rate constant for deactivation by dioxygen (kQ: (Pd)2DPB, 2.98x10(9); (Pd)2DPSN, 3.99x10(9); (Pd)2DPX, 6.94x10(9); (Pd)TPP, 8.95x10(9); (Pd)2DPS, 8.95x10(9) M-1 s-1) of (Pd)2DPSN, which exhibits an intense phosphorescence at 699 nm, was compared to those observed for (Pd)TPP, (Pd)2DPS, (Pd)2DPX, and (Pd)2DPB (TPP2-=tetraphenylporphyrin dianion, DPS4-=4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene tetraanion, DPX4-=4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene tetraanion, and DPB4-=1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene tetraanion). These collision-induced deactivation data were interpreted by estimating a series of physical parameters such as the surface area and bisporphyrin radii, the diffusion coefficient of the bismacrocycles, and the theoretical deactivation efficiency for the five compounds addressing the role of steric hindrance of the macrocycles on each other and the aryl groups at the meso positions. For sensing purposes, (Pd)2DPX is characterized by a Stern-Volmer constant kSV of 2.91x10(6) M-1, placing the lower detection limit for [O2] in solution at 0.58 ppm, which is better than that for (Pd)TPP (kSV=2.31x10(6) M-1; lower detection limit of 0.73 ppm), the classically used monoporphyrin complex. 相似文献